Over the past decade, researchers have shown an increased interest in the field of highly porous materials. This dissertation herein will mainly focus on design and post-synthetic modification of two types of porous materials, such as Metal-Organic Frameworks (MOFs) and Porous Coordination Cages (PCCs) for optimizing guest-host interaction. In chapter I, an overview of the discovery of these porous materials is provided. Their properties and application were discussed. This chapter is concluded by defining specific aims of the subsequent research. One of the drawbacks faced by MOFs is the difficulty in synthesizing frameworks that have a large pore size yet maintain framework stability under harsh conditions. To fulfill this challenge, a simple methodology for the generation of ordered mesopores in an inherently microporous MOF through Soxhlet extraction is discussed in chapter II. This innovative method demonstrates a simple and reproducible process that results in a material that possesses the benefits of mesoporous while borrowing the robustness of a micropore framework. While many mesoporous MOFs have demonstrated good methane uptake, the stability of those MOFs is an issue when unrefined natural gases are attempted to capture. In this chapter, I also report a way to overcome this problem by choosing a stable MOF and applying a post-treatment method by doping long-chain hydrocarbon in the MOF. By applying this process, we observed hydrocarbon doping improves the methane uptake performance for the material. Based on these results, in chapter III, I discuss the investigation of the in-situ functionalization with alkyl chains and even more polar and non-polar groups during the MOF synthesis by using Ligand-Fragment Co-Assembly that will provide the additional steric and electronic interactions necessary to enhance gas binding. In chapter IV, I discuss about another class of porous material PCCs for first row transition metal nanoparticle encapsulation. Design of a series of PCC cages and efforts towards first-row transition metal encapsulation are detailed in this chapter. Finally, a synopsis of the research and opinions on future directions in this field are provided. Overall, my results lay the foundation for optimized post-synthetic modification techniques in porous materials for gas storage and catalysis.
